WO2007097305A1

WO2007097305A1 - Method for producing thermosetting resin, thermosetting resin, thermosetting composition containing same, molded body, cured body, and electronic device containing those

Info

Publication number: WO2007097305A1
Application number: PCT/JP2007/053044
Authority: WO
Inventors: Yuji Eguchi; Kazuo Doyama; Hatsuo Ishida
Original assignee: Sekisui Chemical Co., Ltd.
Priority date: 2006-02-20
Filing date: 2007-02-20
Publication date: 2007-08-30
Also published as: JPWO2007097305A1; US20090054614A1; TW200804444A; JP4248592B2; CN101421324A; KR100977927B1; KR20080094071A; TWI339665B

Abstract

Disclosed is a method for producing a thermosetting resin which has excellent heat resistance and good electrical characteristics, while being improved in brittleness. Also disclosed is a thermosetting resin obtained by such a method. Specifically disclosed is a method for producing a thermosetting resin having a dihydrobenzoxazine ring structure, wherein (a) a polyfunctional phenol compound represented by the general formula (I) below, (b) a diamine compound represented by the general formula (II) below, and (c) an aldehyde compound are heated and reacted with each other. [Chemical formula 1] (I) (II) (In the formulae, X represents an organic group containing an aromatic ring and having 6 or more carbon atoms; and Y represents an organic group having 5 or more carbon atoms. Both X and Y may have N, O or F as a heteroatom. The benzene rings on both sides of X and Y are respectively bonded to different atoms in X and Y.)

Description

Specification

Method for producing thermosetting resin, thermosetting resin, thermosetting composition containing the same, molded product, cured product, and electronic device including them

Technical field

[0001] The present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, and the thermosetting resin. The present invention relates to a composition containing the same, a molded body thereof, a cured body, and an electronic device including them.

Background art

[0002] Conventionally, thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, bismaleimide resin, and the like are based on their thermosetting properties. It is used in a wide range of industrial fields due to its excellent chemical properties, heat resistance, mechanical strength, and reliability.

However, phenol resin and melamine resin produce volatile by-products upon curing, epoxy resin and unsaturated polyester resin have poor flame retardancy, and bismaleimide resin is very expensive. There are some disadvantages.

[0004] In order to eliminate these drawbacks, dihydrobenzoxazine ring compound undergoes ring-opening polymerization reaction and thermosetting without generation of volatile matter causing problems ( Hereinafter, benzoxazine compounds may be abbreviated). In addition to the basic characteristics of thermosetting resin as described above, benzoxazine compounds have excellent storage stability, a relatively low viscosity when melted, and a wide range of molecular design freedom. It is a rosin with advantages. Such a benzoxazine compound is disclosed, for example, in JP-A-49-47378 (Patent Document 1).

[0005] In addition, signal transmission by increasing the density (miniaturization) of electronic devices' components in recent years and improving dielectric properties (to reduce dielectric constant and dielectric loss) to cope with higher transmission signal speeds. Improvements in speed and high-frequency characteristics are required.

[0006] Further, as a raw material of thermosetting resin having such excellent dielectric properties,

Dihydrobenzoxazine compounds represented by (1) and formula (2) are known (for example, non-specific (See Permissible Literature 1 and 2)

[0007] [Chemical 1]

Ph

[0008] [Chemical 2]

[0009] The resin obtained by ring-opening polymerization of the benzoxazine ring of the powerful dihydrobenzoxazine compound is not accompanied by the generation of volatile components during thermal curing, and is also excellent in flame retardancy and water resistance. It is.

[0010] However, although the above-mentioned conventional dihydrobenzoxazine compound has excellent dielectric properties among the thermosetting resins as described above, it has responded to the recent increase in performance of electronic devices * parts. Accordingly, higher dielectric properties are desired. For example, for a resin material of a multilayer substrate that constitutes a package of an IC such as a memory or a logic processor, the dielectric constant is 3.5 or less as a characteristic at 100 MHz and 1 GHz at an ambient temperature of 23 ° C, and The dielectric loss under the same conditions is required to be not more than 0.015 in terms of the dielectric loss tangent value.

[0011] Further, in view of the technical trend expected in the future, a trend toward further lower dielectric loss is required. In the direction. In other words, the dielectric loss usually tends to be proportional to the frequency and the dielectric loss tangent of the material, while the frequency used in electronic equipment and components tends to be higher. The demand is getting higher.

[0012] In response to demands for improving electrical characteristics, heat resistance, toughness, and flexibility, Japanese Patent Laid-Open No. 2005-239827 proposes a technique for dealing with fine processing ( Patent publication 2). However, this technology is disadvantageous in terms of hygroscopicity and electrical properties due to the presence of free OH groups.

[0013] In addition, JP 2003-64180 A discloses a thermosetting resin having a benzoxazine structure in the main chain and excellent in heat resistance and mechanical properties, in which a bifunctional phenolic part is disclosed. Are bonded with a siloxane group (Patent Document 3).

[0014] The above document discloses a long-chain aromatic diamine as one that imparts flexibility. As a result of the study by the present inventors, the combination described in the above document does not provide sufficient flexibility. It has been found. Also, those containing a highly polar group such as a sulfone group are disadvantageous in terms of electrical characteristics.

[0015] Non-Patent Document 3 and Patent Document 4 also disclose a benzoxazine compound having a specific structure having a benzoxazine structure in the main chain. However, Non-Patent Document 3 discloses only compounds, and does not describe characteristics evaluation. Furthermore, Patent Document 4 does not disclose guidelines for improving heat resistance or imparting flexibility and composite materials. Further, Non-Patent Document 4 discloses a decomposition mechanism of a cured product of a benzoxazine compound. The phosphorus and monofunctional talesols described in this document have volatility at low temperatures. Furthermore, Patent Document 5 discloses a method for producing a benzoxazine compound in which both diamine and monoamine are essential as amines. However, the use of monoamine is disadvantageous from the viewpoint of heat resistance.

Patent Document 1: JP-A-49-47378

Patent Document 2: Japanese Patent Laid-Open No. 2005-239827

Patent Document 3: Japanese Patent Laid-Open No. 2003-64180

Patent Document 4: Japanese Patent Laid-Open No. 2002-338648

Patent Document 5: Japanese Patent No. 3550814 Non-Patent Document 1: Konishi Chemical Industry Co., Ltd. website [Searched on November 24, 2005], Internet '~~ Not ^ ^ URL: nttp: //www.konishi-chem.co.jp/cgi-data/ / pdf / pdf_2.pdf> Non-Patent Document 2: Shikoku Kasei Kogyo Co., Ltd. website [Searched 24 November 2005], Internet URL: nttp: / 1 www.shikoku.co.jp/ products /benzo.html>

Non-Special Reference 3: Benzoxazine Monomers and Polymers: New Phenolic Resins by Ring

-Opening Polymerization, J.P.Liu and H. Ishiaa, "The Polymeric Materials Encyclopedia," J.C.Salamone, Ed., CRC Press, Florida (1996) pp.484—494

Non-Patent Document 4: H.Y 丄 ow and H.Ishida, Polymer, 40, 4365 (1999)

Disclosure of the invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a method for producing a thermosetting resin having excellent heat resistance, excellent electrical characteristics, and greatly improved brittleness, and a thermosetting resin obtained thereby. That's true.

[0017] Further, another object of the present invention is to provide a composition containing the above thermosetting resin, a molded product thereof, a cured product, and an electronic device containing them.

Means for solving the problem

[0018] As a result of intensive studies, the present inventor, from the viewpoint of improving heat resistance, does not use an aliphatic amine or an aromatic monoamine, but uses a specific aromatic diamine and a specific phenol compound, and is heat-cured. The knowledge that the manufacturing method of a characteristic rosin can achieve the said objective was acquired. The present invention is based on such knowledge. That is, the configuration of the present invention is as follows.

Hereinafter, “benzoxazine resin” refers to a resin having the dihydrobenzoxazine ring structure.

[0019] 1. a) A polyfunctional phenolic compound represented by the following general formula (I), b) a diamine compound represented by the following general formula (II), and c) an aldehyde compound are reacted by heating. A process for producing a thermosetting resin having a dihydrobenzoxazine ring structure characterized by the above.

[0020] [Chemical 3] HO

(I)

[Wherein X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[0021] [Chemical 4]

[Wherein Υ is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[0022] 2. The above-mentioned 1, wherein X in the general formula (I) is bonded to the para-position with respect to the OH groups of both benzene rings, and the structure of X is any of the following: A method for producing a thermosetting resin.

[0023] [Chemical 5]

3. The method for producing a thermosetting resin according to 1 above, wherein X in the general formula (I) has a structure shown below.

[Wherein n represents an integer of 0 to 10. ]

4. The method for producing a thermosetting resin according to 1 above, wherein X in the general formula (I) has a structure shown below.

[Chemical 7]

[Wherein n represents an integer of 0 to 10. ]

5. The method for producing a thermosetting resin according to 1 above, wherein X in the general formula (I) has a structure shown below.

[Chemical 8]

[Wherein n represents an integer of 0 to 10. ]

6. a) Polyfunctional phenolic compound represented by the following general formula (I), b) Diamine compound represented by the following general formula (II), c) Aldehydic compound, and the following general formula (III 2. The method for producing a thermosetting resin according to the above 1, having a dihydrobenzoxazine ring structure, wherein the monofunctional phenol represented by formula (1) is reacted by heating. [0028] [9]

[0029] [Chemical 10]

[Chemical 11]

… (I I I)

[In the formula, Z is an organic group having 4 or more carbon atoms and has N, 0, F as heteroatoms. ]

[0031] 7. In the monofunctional phenol compound represented by the general formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is represented by the following formula: 6. The method for producing a thermosetting resin according to 6 above, wherein

[0032] [Chemical 12] HC— C 1 CK

CH

[n represents an integer of 0 to 10. ]

[0033] 8. In the monofunctional phenolic compound represented by the general formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is represented by the following formula: 6. The method for producing a thermosetting resin according to 6 above, wherein

[0034] [Chemical 13]

[0035] 9. The method for producing a thermosetting resin according to 1 above, wherein the Y force in the general formula (II) is a group represented by the following formula.

[Chemical 14]

I ³

0-CH ^ C-CH O- 2 I ²

CH

[0036] 10. The Y force in the general formula (II) The method for producing a thermosetting resin according to 1 above, comprising one benzene ring.

[0037] 11. Y in the general formula (II) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta or para position with respect to the NH groups of the benzene rings on both sides thereof. Do the above

2

10. A method for producing a thermosetting resin according to 10.

[0038] [Chemical 15]

[0039] 12. The Y force in the general formula (II) The method for producing a thermosetting resin according to 1 above, comprising at least two benzene rings.

[0040] 13. Y in the general formula (II) is one or more groups selected from the group of the following formulas;

Bonded to the meta or para position to the NH group of the benzene ring on both sides of Y,

2

A method for producing the thermosetting resin as described.

[0041] [Chemical 16]

[0042] 14. A thermosetting resin characterized by being a thermosetting resin having a dihydrobenzoxazine structure represented by the following general formula (IV).

[0043] [Chemical 17]

V)

[Wherein X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X.

Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m represents an integer of 1 to 50. ]

[0044] 15. X in the general formula (IV) has any structure of the following group of X :, and Y in the general formula (IV) is any of the following groups of Y: 15. The thermosetting resin according to the above 14, having a structure.

[0045] [Chemical 18]

[6ΐ ^] [9 rinse]

M70CS0 / .00Zdf / X3d S0C.60 / .00Z OAV

[0047] 16. A thermosetting composition comprising at least the thermosetting resin according to 14.

[0048] 17. A molded body obtained by semi-curing or not curing the thermosetting composition according to 16 above.

[0049] 18. A cured product obtained from the thermosetting resin according to 14 above.

[0050] 19. A cured product obtained from the thermosetting composition according to 16 above.

[0051] 20. An electronic component comprising the cured product according to 18 or 19 above.

[0052] 21. A thermosetting resin manufactured by the manufacturing method described in 1 above.

[0053] 22. A thermosetting composition comprising at least the thermosetting resin according to 21 above.

[0054] 23. A molded article obtained by semi-curing or not curing the thermosetting composition according to 22 above.

[0055] 24. A cured product obtained from the thermosetting resin described in 21 above.

[0056] 25. A cured product obtained from the thermosetting composition according to 22 above.

[0057] 26. An electronic component comprising the cured product according to 24 or 25.

The invention's effect

[0058] According to the present invention, a production method capable of obtaining a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, and a thermosetting cake obtained by the production method. Fats, compositions containing the greaves, molded articles, cured bodies, and electronic devices containing them are provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0059] Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. [Method for producing thermosetting resin]

The method for producing a thermosetting resin according to the present invention includes: a) a polyfunctional phenol compound represented by the following general formula (I); b) a diamine compound represented by the following general formula (II); and c). An aldehyde compound is heated and reacted. And the thermosetting rosin which has a dihydrobenzoxazine ring structure can be obtained with the manufacturing method of this invention. The resulting thermosetting resin has excellent heat resistance, good electrical properties, and greatly improved brittleness.

[0060] [Chemical 20]

[Wherein, X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]

[Chemical 21]

[Wherein Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]

[0062] In the present invention, the polyfunctional phenolic compound represented by the general formula (I) is used as the component a). The strong polyfunctional phenol compound is not particularly limited as long as it is a bifunctional or higher polyfunctional phenol. In addition, these bifunctional or higher polyfunctional phenols are used alone or in combination of two or more.

[0063] The polyfunctional phenolic compound of component a) used in the present invention has an X force X in the general formula (I) of 6 or more carbon atoms including an aromatic ring, preferably 8 or more carbon atoms, Preferably 12 to 12 carbon atoms

21 organic groups. X may have N, 0, or F as a hetero atom.

[0064] X is bonded to the OH group of the benzene ring on both sides in the para position, particularly in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties. In addition, it is preferable that the structure of X is any one or any of the following.

[0065] [Chemical 22]

In addition, X preferably has the structure shown below in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties.

[Chemical 23]

[Wherein n represents an integer of 0 to 10, preferably 0 to 5. ]

[Chemical 24]

[Wherein n represents an integer of 0 to 10, preferably 0 to 5. ]

[Chemical 25]

[Wherein n represents an integer of 0 to 10. ]

[0069] Specific examples of such polyfunctional phenolic compounds of component a) include 4, 4 '[1, 4 phenol-lenbis (1-methylethylidene)] bisphenol (Mitsui Chemicals). Manufactured by: Bisphenol P), 4, 4 '[1, 3 Phenolenbis (1-methylethylidene)] bisphenol (Mitsui Chemicals Co., Ltd .: Bisphenol M), Biphenol-Novolac type phenol resin (Maywa Kasei: MEH7851), xylylene novolac-type phenol resin (Maywa Kasei: MEH7800), and the like. These polyfunctional phenol compounds are used singly or in combination.

In the present invention, the diamine compound represented by the general formula (II) is used as the component b). Powerful jaminy compounds are essential, especially in terms of improving flexibility.

[0071] The diamine compound of component b) used in the present invention is a long-chain aromatic diamine compound, and Y in the general formula (II) has 5 or more carbon atoms, preferably 5 to 5 carbon atoms. 20, more preferably 5 to 15 organic groups. If Y has N, 0, or F as a heteroatom, the electrical characteristics can be improved. In addition, the benzene rings on both sides of Y are not bonded to the same atom in Y.

[0072] Y is preferably a group represented by the following formula, particularly in terms of solubility during synthesis of thermosetting resin, mechanical properties of the cured product, and electrical properties.

[Chemical 26]

I ³

— 0-CH ^ -C-CH O—

2 I ²

CH ₃ [0073] Further, Y preferably contains one benzene ring from the viewpoints of heat resistance, mechanical properties, and electrical properties of the cured product.

[0074] Specific examples of Υ containing one benzene ring are selected from the group of the following formulas-and the 以 is a meta-position or

2

And the like bonded to the position. It is preferable that the cocoon has these groups because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.

[0075] [Chemical 27]

[0076] The thermosetting resin having a dihydrobenzoxazine ring structure having one or more groups selected from the above group has other groups [for example, bisphenol 8-8? Compared with (= 2, 2 bis [4 (4 aminophenoxy) phenol] propane) (2 nuclei + 4 nuclei)], the following points are superior.

(1) Compared with 2 nuclei and 4 nuclei, it becomes 3 nuclei 3 nuclei or 3 nuclei 4 nuclei, and the minimum distance of the benzoxazine ring that becomes a crosslinking point at the time of curing is increased to 3 nuclei, so flexibility is increased.

(2) For polyfunctional phenols with a trifunctional or higher functional group (ΟΗ), the bifunctional group is composed of benzoxazine rosin in a straight line and is less susceptible to gelation and has a poor synthesis. .

(3) Comparing the para bisphenol Ρ and the meta bisphenol Μ, it is not clear whether it is caused by the low density due to the size of the free volume, but the dielectric constant tends to be low. In addition, it is easy to solvate because of its high molecular strength, and the solubility in organic solvents is high.

[0077] In addition, soot has a small amount of benzene ring, particularly in terms of heat resistance, mechanical properties, and electrical properties of the cured product. It is preferable to include at least two.

[0078] Specific examples of those in which Y contains at least two benzene rings are selected from the group of the following formulas:-or more groups, and meta-positions or NH groups on the benzene rings on both sides of Y.

2

Examples include those that bind to the position. When Y has these groups, it is particularly preferable because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.

[0079] [Chemical 28]

[0080] Specific examples of the diamine compound of component b) include 1,3 bis (3 aminophenoxy) benzene, 1,3 bis (4 aminophenoxy) benzene, 1,4 bis (3 aminophenoxy). ) Benzene, 1, 4 bis (4 aminophenoxy) benzene, 1, 3 bis (4 aminophenoxy) neopentane, 2, 2 bis [4— (3-aminophenoxy) phenol] propan, 2, 2 bis [4— (4 aminophenoxy) phenol] propane, bis [(3 aminophenoxy) phenol] biphenyl, bis [(4-aminophenoxy) phenol] biphenyl, 2, 2-bis [4 one (4 Aminophenoxy) phenol] hexafluoropropane, bis [3- (3-aminophenoxy) phenol] ether, bis [3- (4 aminophenoxy) phenol] ether, bis [4- (3- Aminophenoxy) phenol] ether, The [4 i (4-aminophenoxy) phenyl] ether, and the like. These diamine compounds are used alone or in combination of two or more.

[0081] The aldehyde compound of component c) used in the present invention is not particularly limited, but formaldehyde is preferred. Examples of the formaldehyde include paraformaldehyde, which is a polymer thereof, and an aqueous solution. Can be used in the form of formalin Noh. The reaction progresses more slowly when using norformaldehyde. Further, as other aldehyde compounds, acetoaldehyde, propionaldehyde, butyl aldehyde and the like can be used.

[0082] As another embodiment of the production method of the present invention, a monofunctional phenolic compound represented by the following general formula (III) is further used as the component d) together with the components a) to c) described above. It is possible to provide a method to do this. When the monofunctional phenolic compound of component d) is used, processability such as solubility can be secured.

[0083] [Chemical 29]

[0084] The monofunctional phenolic compound as component d) has a large side chain molecular weight, and Z in the general formula (III) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 to 20 organic groups. As the number of carbon atoms increases, the free volume increases and the dielectric constant may decrease. Z may have N, 0, or F as a hetero atom.

[0085] In the monofunctional phenolic compound represented by the general formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: It is preferable that

[0086] [Chemical 30]

H C— C— CK

[n represents an integer of 0 to 10. ]

[0087] Among these, Z is preferably a group substituted in the para position with respect to the OH group and represented by the following formula.

[0088] [Chemical 31]

H ₃ CC-CH ₃

CH ₃

[0089] Further, Z is mainly a para-position with respect to the OH group in the benzene ring in the general formula (III) in terms of dielectric properties such as non-volatility at high temperature, dielectric constant and dielectric loss tangent. And a group represented by the following formula is preferred.

[0090] [Chemical 32]

I

H ₃ CC-CH,

CH

I ²

HC-C-CH- 3 I ³

CH ₃

[0091] Further, the substituent Z of the monofunctional phenol compound represented by the general formula (III) is the above general formula in terms of dielectric properties such as non-volatility, dielectric constant and dielectric loss tangent at high temperatures. The benzene ring in (III) is preferably bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula:

[0092] [Chemical 33]

[0093] Specific examples of the monofunctional phenolic compound of component d) include 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenolphenol, 4-phenolphenol. 2-benzylphenol, 4-benzylphenol, 2-hydroxybenzo Phenone, 4-hydroxybenzophenone, 4-hydroxybenzoic acid phenol ester, 4-phenoxyphenol, 3-benzyloxyphenol, 4-benzyloxyphenol, 4- (1, 1, 3, 3-tetramethylbutyl) phenol, 4-a-tamylphenol, 4-adamantylphenol, 4-trimethylmethylphenol and the like. These monofunctional phenol compounds are used singly or in combination.

[0094] In the production method of the present invention, for example, the a), b) and c) components, and if necessary, the d) component can be reacted by heating in a suitable solvent.

[0095] In the production method of the present invention, a monofunctional phenolic compound or a polyfunctional phenolic compound may be further added.

Examples of monofunctional phenolic compounds that can be additionally added here include monofunctional phenols as described above, and examples of polyfunctional phenolic compounds include polyfunctional phenols as described above, and 4 , 4'-biphenol, 2, 2, -biphenol, 4, 4'-dihydroxydiphenyl ether, 2, 2, -dihydroxydiphenyl ether, 4, 4'-dihydroxydiphenyl methane, 2, 2, 1-dihydroxydiphenylmethane 2, 2 bis (4 hydroxyphenyl) bread, 4, 4, 1-dihydroxybenzophenone, 1, 1-bis (4 hydroxyphenyl) ethane, 1, 1-bis (4 hydroxyphenol) ) Propane, 1,1-bis (4-hydroxyphenol) butane, 2,2-bis (4-hydroxyphenol) butane, 1,1-bis (4-hydroxyphenol) but-2-methylpropane, 1, 1—Bis (4 Hydroxyphenol) cyclohexane, 1,1 bis (4 hydroxyphenol) cyclopentane, 1,1 bis (4 hydroxyphenol) —1-phenol ethane, bis (4-hydroxyphenol) Diphenylmethane, 9, 9-bis (4-hydroxyphenol) fluorene, 2, 2 bis (4-hydroxyphenol) hexafluorate propane, 1, 3 bis (4 hydroxyphenoxy) benzene, 1 , 4 bis (3 hydroxyphenoxy) benzene, 2, 6 bis ((2 hydroxyphenol) methyl) phenol and the like.

[0096] The solvent used in the production method of the present invention is not particularly limited, but the one having a good solubility of the raw material phenolic compound is a diamine compound and the product polymer is good. However, it is easy to obtain a polymer having a high degree of polymerization. Examples of such solvents include aromatic solvents such as toluene and xylene, halogen solvents such as chloroform, dichloromethane, and THF. And ether solvents such as dioxane.

[0097] The reaction temperature and reaction time are not particularly limited, but the reaction may usually be carried out at a temperature of room temperature to about 120 ° C for about 10 minutes to 24 hours. In the present invention, it is particularly preferable to react at 30 to 110 ° C. for 20 minutes to 9 hours because the reaction proceeds to a polymer capable of expressing the function as the thermosetting resin according to the present invention. . At high temperatures and for long-term reactions, the potential for gelling due to the formation of higher molecular weight resins or three-dimensional cross-linked polymers is the desired low temperature. However, it is desirable to increase the reaction time or the reaction temperature at a point where the molecular weight is sufficiently high for coating and the resin cannot be synthesized in a short reaction.

[0098] Further, removing water generated during the reaction out of the system is also an effective technique for promoting the reaction. For example, a polymer can be precipitated by adding a large amount of a poor solvent such as methanol to the solution after the reaction, and the desired polymer can be obtained by separating and drying the polymer.

[0099] It should be noted that monofunctional amine compounds, trifunctional amine compounds, and other diamine compounds may be used as long as the properties of the thermosetting resin of the present invention are not impaired. When a monofunctional amine is used, the degree of polymerization can be adjusted, and when a trifunctional amine is used, a branched polymer is obtained. The physical properties can be adjusted by using other diamine compounds in combination. These can be used at the same time as the diamine compound essential to the present invention. In consideration of the order of the force reaction, they can be added to the reaction system and reacted later.

[0100] [Thermosetting resin]

The thermosetting resin of the present invention includes a structure represented by the following general formula (IV).

The thermosetting resin of the present invention can also be obtained by the above-described method for producing a thermosetting resin.

[Chemical 34]

(I V)

[Wherein, X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m represents an integer of 1 to 50. ]

The structure can be identified by IR, NMR, GC-MS and other techniques.

When m is 2 or more, X may be different in the synthesized thermosetting resin, which need not all be the same. Similarly, when m is 2 or more, Y may be different in the synthesized thermosetting resin, and in the general formula (IV), X may be the following: It is preferable that X has a structure of any of the groups of X: and Y preferably has a structure of any of the following groups of Y :.

[Chemical 35]

[0103] [Chemical 36]

[0104] The thermosetting resin of the present invention has particularly excellent heat resistance, good electrical properties, and greatly improved brittleness.

[Thermosetting composition]

The thermosetting composition of the present invention contains at least the thermosetting resin described above. The thermosetting composition according to the present invention preferably contains the thermosetting resin as a main component, for example, the thermosetting resin as a main component, and other components as other components. What contains a thermosetting resin is mentioned.

[0106] Other thermosetting resins as subcomponents include, for example, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, key resin resins, and melamine resins. Examples thereof include fats, urea resins, aryl resins, phenol resins, unsaturated polyester resins, bismaleimide resins, alkyd resins, furan resins, polyurethane resins, and alin resins. Among these, epoxy resin, phenol resin, and thermosetting polyimide resin are more preferable from the viewpoint of further improving the heat resistance of the molded article formed with this composition strength. These other thermosetting resins may be used alone or in combination of two or more. Further, in the thermosetting composition according to the present invention, it is preferable to use a compound having at least one, preferably two dihydrobenzoxazine rings in the molecule described in the known literature as an accessory component. . As the compound having at least one dihydrobenzoxazine ring in the molecule, only one kind may be used or two or more kinds may be used in combination.

[0107] In addition, the thermosetting composition according to the present invention includes a flame retardant, a nucleating agent, an anti-oxidation agent (anti-aging agent), a heat stabilizer, a light stabilizer, and an ultraviolet absorber as necessary. Various additives such as an agent, a lubricant, a flame retardant aid, an antistatic agent, an antifogging agent, a filler, a softener, a plasticizer, and a colorant may be contained. These may be used alone or in combination of two or more. In preparing the thermosetting composition according to the present invention, a reactive or non-reactive solvent can also be used.

[0108] The thermosetting resin composition according to the present invention may be formed into a film by dissolving the thermosetting resin composition in an organic solvent, casting it, and drying the solvent.

It is preferable that the thermosetting resin or thermosetting resin composition that is useful for the present invention has a higher solubility in an organic solvent such as toluene. This is a cast in solution When forming a film, the amount of solvent can be reduced, and if the solvent content is low, the energy for solvent evaporation is small, the drying time is short, and there is no blistering due to rapid drying. This is because there is an effective advantage.

[0109] [Molded body]

The molded body according to the present invention is obtained by semi-curing or not curing the thermosetting resin described above or a thermosetting composition containing the same.

Here, “semi-curing” is to stop the curing of the thermosetting resin at an intermediate stage, and to a state where the curing can proceed further. Semi-cured thermosetting resin is sometimes referred to as a stage. (The following description is also synonymous)

As the molded article of the present invention, the thermosetting resin described above has moldability even before curing, and therefore the dimensions and shape thereof are not particularly limited. For example, a sheet (plate), a block, And other parts (for example, an adhesive layer) may be provided. The sheet-like material may be formed on a support film.

[0110] [Hardened body]

The cured body according to the present invention is obtained by curing the thermosetting resin having thermosetting property, the base composition having thermosetting property, and the molded body having thermosetting property by heating. As the curing method, any conventionally known curing method can be used. In general, heating may be performed at about 120 to 300 ° C. for several hours, but the heating temperature may be lower or the heating time may be increased. If insufficient, in some cases, curing may be insufficient and mechanical strength may be insufficient. Also, if the heating temperature is too high or the heating time is too long, in some cases, side reactions such as decomposition may occur and the mechanical strength may be disadvantageously reduced. Therefore, it is desirable to select appropriate conditions according to the characteristics of the thermosetting compound to be used.

[0111] When curing is performed, an appropriate curing accelerator may be added. As the curing accelerator, any curing accelerator generally used in ring-opening polymerization of dihydrobenzoxazine compounds can be used. For example, polyfunctional phenols such as catechol and bisphenol A can be used. , Sulfonic acids such as ρ-toluenesulfonic acid, p-phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid, adipic acid, cobalt (II) acetyl cetate, aluminum (III) acetyl Setonate, Zirconium (IV) Acetylacetate Metal complexes such as nates, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide and iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diazabicyclodecene, diazabicyclononene and their salts And phosphorous compounds such as triphenylphosphine, triphenylphosphine'benzoquinone derivative, triphenylphosphine'triphenylboron salt, tetraphenylphosphonium'tetraphenylporate, and derivatives thereof. These may be used alone or as a mixture of two or more.

[0112] The addition amount of the curing accelerator is not particularly limited. However, if the addition amount is excessive, the dielectric constant of the molded article increases, the dielectric loss tangent is increased, and the mechanical properties are adversely affected. In general, therefore, it is desirable to use a curing accelerator at a ratio of preferably 5 parts by weight or less, more preferably 3 parts by weight or less, with respect to 100 parts by weight of the thermosetting resin.

[0113] The cured product of the present invention comprising the thermosetting resin or the thermosetting composition thus obtained as described above has a benzoxazine structure in the polymer structure, thereby realizing excellent dielectric properties. can do.

[0114] Further, the cured body of the present invention is excellent in reliability, flame retardancy, moldability and the like based on the thermosetting properties of the thermosetting resin or the thermosetting composition. In addition, since the glass transition temperature (Tg) is high, it can be applied to parts where stress is applied or moving parts, and volatile by-products are not generated during polymerization. Volatile by-products do not remain in the molded body, which is preferable for hygiene management.

[0115] The cured product of the present invention is preferably used for applications such as electronic components and electronic devices and materials thereof, multilayer boards, copper-clad laminates, sealants, adhesives, and the like that particularly require excellent dielectric properties. Can do.

Here, the electronic component includes a substrate or an IC element, a resistor, a capacitor, a coil, a substrate having an electrical conductor layer on the surface of the cured body of the present invention, and a terminal for electrical connection such as a flexible substrate. Refers to the board on which is mounted.

[0116] Typical examples of the present invention are shown below, but the present invention is not limited thereto. Example 1

[0117] α, α, monobis (4-hydroxyphenol) -1,4-diisopropylbenzene (98% manufactured by Tokyo Kosei Co., Ltd.) 21.21 g (0.06 mol), 2 , 2-bis [4- (4-Aminophenoxy) phenol] propane (Tokyo Kasei, 98%) 25. 13 g (0. 06 mol), paraformaldehyde (Wako Pure Chemical, 94%) 8. 05 g ( 0.25 mol) was added, and the reaction was carried out for 6 hours under reflux while removing the generated water. The reaction scheme is shown below. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 40.78 g of thermosetting resin mainly composed of a benzoxazine compound having the following structure.

When measuring molecular weight, Shimadzu GPC (gel permeation chromatograph) is equipped with degasser DGU-12A, pump LC-10AD, controller SCL-10A, detector (RI) RID-10A, column oven CTO-10AS. I went there. Two columns, S HODEX KF-804L (exclusion limit of 400,000), were used in series, and the solvent was THF, the flow rate was 1 ml / min, and the column temperature was 40 ° C. Standard polystyrene (Tosohichi) 354,000, 189000, 98900, 37200, 17100, 9830, 5870, 2500, 1050, 500 Polystyrene was used to create a calibration equation with a cubic equation. The molecular weight of the resin synthesized based on the calibration formula was measured. In the molecular weight measurement of the obtained rosin, the weight average molecular weight was 19,500 o

[0118] [Chemical 37]

M70CS0 / .00Zdf / X3d οε S0C.60 / .00Z OAV Example 2

[0119] The polymer obtained in Example 1 was held at 180 ° C for 1 hour by a hot press method to obtain a 0.5 mmt sheet-like cured body. The obtained cured product was transparent, brown and uniform, and had excellent flexibility.

Measure the dielectric constant and dielectric loss tangent at 23 ° C, 100 MHz, and 1 GHz by the capacitance method using the dielectric constant measurement device (trade name “RF impedance material material analyzer E4991AJ” manufactured by AGILENT) The results are shown in Table 1. The cured product of Example 2 showed good characteristics in both dielectric constant and dielectric loss tangent.

The obtained sheet was cut into fine pieces and 5% weight reduction temperature (10% CZmin) in an air atmosphere by the TGA method using the product name “DTG-60” manufactured by Shimadzu Corporation. Td 5) was evaluated. The cured product of Example 2 showed a good value of Td5 of 415 ° C.

[0120] [Table 1] Table 1. Example 2

Example 3

[0121] In Example 1, 21.21 g (0.06 mol) of bisphenol M (Mitsui Chemicals) was used in place of 1,4,4-diisopropylbenzene. A thermosetting resin was synthesized in the same manner as in Example 1 except that. The yield was 40.56g. The weight average molecular weight of the obtained rosin was 10,600 as measured by GPC. Example 4

[0122] In the same manner as in Example 2, the grease of Example 3 was evaluated. The results are summarized in Table 2. The thermosetting resin of Example 3 showed good results in both electrical characteristics and heat resistance.

[0123] [Table 2] Table 2. Example 4

Example 5

[0124] In the black mouth form, a, a, —bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (manufactured by Tokyo Kaisei, 98%) 20. 68 g (0. O585 mol), 4 — A-cumino leunore (manufactured by Tokyo Goseisei, 98%) 2. 82 g (0. O13 mol), a, α, monobis (4-aminophenenole) 1, 1, 4-diisopropylbenzene (Tokyo Kasei) 98%) 22.85 g (0.O65 mol), paraformaldehyde (Wako Pure Chemicals, 94%) 8.72 g (0.27 mol) was added, and the reaction was performed for 6 hours under reflux while removing the generated water. I let you. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 37.21 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

As a result of GPC molecular weight measurement, the weight average molecular weight was 7,200. Example 6

[0125] In the same manner as in Example 2, the grease of Example 5 was evaluated. The results are summarized in Table 3. The thermosetting resin of Example 3 showed good results in both electrical characteristics and heat resistance.

[0126] [Table 3]

Table 3. Example 6

Example 7

In black form, biphenyl novolac type phenol resin (Maywa Chemical Co., Ltd. ΓΜΕΗ7851 SS ”, OH S204) 30.00 g, α, α '-bis (4-aminophenol) — 1, 4-diisopropyl pentbenzene (Tokyo Kasei) 98%) 21.08g (0.061mol), paraformaldehyde ( (Wako Pure Chemicals, 94%) 8.13 g (0.25 mol) was added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 45.52 g of thermosetting resin having a benzoxazine structure. Example 8

In Example 7, instead of α 1, α, monobis (4-aminophenol) 1,4-diisopropylbenzene (Tokyo Kasei, 98%), 2, 2bis [4 mono (4 aminophenoxy) [Fuel] propane (manufactured by Wakayama Seika Co., Ltd., 99.9%) A thermosetting resin having a benzoxazine structure was synthesized in the same manner as in Example 7, except that the amount was changed to 24.90 g (0.061 mol). The yield was 45.80g.

Example 9

[0129]

Example 10

[0130] In the same manner as in Example 2, the greaves of Examples 7 and 8 were evaluated. The results are summarized in Table 4.

The thermosetting resin of Examples 9 and 10 showed good results in both electrical characteristics and heat resistance.

[0131] [Table 4] Table 4. Examples 9, 10

Example 11

In chlorohonorem, Bisphenol A (Mitsui Chemicals, 99.5%) 27.86g (0.08mol), Bisanilin M (Mitsui Chemicals, 99.98%), 27.57g (0.08mol), Norajo / remuanolide hydride (manufactured by Wako Pure Chemicals, 94%) 10.73 g (0.34 mol) was added, and the reaction was performed under reflux for 6 hours while removing the generated water. The solution after the reaction is poured into a large amount of methanol to remove the product. Precipitated. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 31.21 g of a thermosetting resin containing a benzoxazine compound having the following structure as a main component. In the molecular weight measurement of the obtained rosin by GPC, the weight average molecular weight was 16,600.

[Chemical 38]

Example 12

[0133] In the same manner as in Example 2, the grease of Example 11 was evaluated. The results are summarized in Table 5.

The thermosetting resin of Example 11 showed good results in both electrical characteristics and heat resistance.

[0134] [Table 5] Table 5. Example 1 2

Example 13

[0135] DPP6085 (Nippon Petroleum, 99%) 30.0 g (0. 086 mol), Bisalin P (Mitsui Chemicals, 99%) 29. 91 g (0. 086 mol) ) Was then stirred, and then paraformaldehyde (Wako Pure Chemicals, 94%) 11.53 g (0.344 mol) was added and reacted under reflux for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 36.27 g of a thermosetting resin containing a benzoxazine compound having the following structure as a main component.

[0136] [Chemical 39]

Example 14

In the same manner as in Example 2, the resin of Example 13 was evaluated. The results are summarized in Table 6. The thermosetting resin of Example 13 showed good electrical properties.

[Table 6] Table 6. Example 1 4

Example 15

[0138] In the black mouth form, α, α, monobis (4-hydroxyphenol) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 20.68 g (0.058 mol), 4-t —Octylphenol (Tokyo Kasei Co., Ltd., 95%) 2. 82 g (0.013 mol), a, α, monobis (4-aminophenol)-1,4-diisopropylbenzene (Tokyo Kasei Co., Ltd., 98% ) 22.85 g (0. 065 mol), paraformaldehyde (manufactured by Wako Pure Chemicals, 94%) 8.72 g (0.27 mol) were added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 41.95 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

Example 16

[0139] In the same manner as in Example 2, the resin of Example 15 was evaluated. The results are summarized in Table 7.

The thermosetting resin of Example 15 showed good results in both electrical characteristics and heat resistance.

[Table 7] Table 7. Example 1 6

Example 17

In the black mouth form, 1, 4, diisopropyl benzene (Tokyo Kasei, 98%) 13. 85 g (0.040 mol), Bisalin M (Tokyo Kasei, 98%) 13. 78g (0.040mol), Norahonole Munoredehyde (manufactured by Kuroko Pure Chemical, 94%) 5. 04g (0.168mol) was added under reflux while removing the generated water. The reaction was performed for 6 hours. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 34.52 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

[Chemical 40]

Example 18

In the same manner as in Example 2, the resin of Example 17 was evaluated. The results are summarized in Table 8. The thermosetting resin of Example 17 showed good results in both electrical characteristics and heat resistance.

[¾8] Table 8. Example 1 8

(Comparative Example 1) [0142] bis— A / MDA (2 nuclei + 2 nuclei)

Bisphenol A (Tokyo Kasei, 98%) 18.45g (0.08mol), 4,4'-Diaminodiphenylmethane (Wako Pure Chemicals, 98%) 16. 19g (0.08mol) ), Paraformaldehyde (94% manufactured by Wako Pure Chemical Industries, Ltd.) 10.73 g (0.336 mol) was added, and the mixture was reacted under reflux for 6 hours while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 26.44 g of thermosetting resin mainly composed of a benzoxazine compound having the following structure.

[0143] [Chemical 41]

(Comparative Example 2)

In the same manner as in Example 2, the resin of Comparative Example 1 was evaluated. The results are summarized in Table 9. The thermosetting resin of Comparative Example 1 was inferior in both electrical properties and heat resistance.

[Table 9] Table 9. Comparative Example 2

(Comparative Example 3)

bis A / BAPP (2 nuclei + 4 nuclei)

Bisphenol A (Tokyo Kasei, 98%), 18.27 g (0.08 mol), 2, 2 bis [4 (4-aminophenoxy) phenol] propane (Tokyo Kasei, 98%) 32. 89 g (0. 08 mol), paraformaldehyde (94% made by Wako Pure Chemical Industries) 10. 73 g (0. 336 mol) The reaction was carried out for 6 hours under reflux while removing generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 39.62 g of a thermosetting resin mainly composed of a benzoxazine compound having the following structure.

[Chemical 42]

(Comparative Example 4)

In the same manner as in Example 2, the resin of Comparative Example 3 was evaluated. The results are summarized in Table 10. The thermosetting resin of Comparative Example 3 was inferior in electrical characteristics and heat resistance, and the film was whitened when bent.

[Table 10]

Table 1 0. Comparative Example 4

Example 19

In the black mouth form, a, _a , —bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22. 98 g (0.065 mol), Bisalin P (Tokyo) Kasei Chemical, 98%) 22.85 g (0.065 mol), Norahonoremua / Redehide (Turoko Mitsuru Pure Chemical, 94%) 8.72 g (0.273 mol) were added under reflux while removing the generated water. The reaction was performed for 6 hours. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 34.52 g of a thermosetting resin containing a benzoxazine compound having the following structure as a main component. The obtained polymer was insoluble in general-purpose solvents such as toluene and DMF. Also, Even if hot pressing was performed, the film could not be formed due to infusibility.

[0149] [Chemical 43]

Example 20

[0150] Using toluene as a solvent, the benzoxazine succinate synthesized in each example so as to be 20%, 30, 30, 40, 50, and 60% by weight was added, and stirred for 24 hours at room temperature to dissolve. I confirmed that.

In the case of benzoxazine succinate of Example 13, 20 to 50% by weight was dissolved even in the confirmation experiment of deviation, and Examples 1, 3, 5, 7, 8, 11, 15, 17 and Comparative Examples 1 and 3 were all dissolved. Nzooxazine rosin was dissolved in 20-60% by weight confirmation experiment. The benzoxazine resin of Example 19 did not dissolve at any of 20 to 60% by weight.

The use of a bent M-form having a substituent at the meta position, such as bisphenol M or bis-line M, improves the solubility even at a high molecular weight.

Example 21

[0151] Sample films were prepared so that the composites of Examples 1, 3, 5, 7, 8, 11, 13, 15, 17 and Comparative Examples 1 and 3 had a width of 10 mm and a thickness of 75. In preparing the sample film, a 50% by weight solution was prepared with toluene having the same weight as that of each resin, and the sample was drawn by an applicator and then removed by drying in an oven to prepare a sample. A bending test was performed on the produced film. In the bending test, the sample film is folded in half and pressed from both sides with a force of 3 kgf, and then the film is spread. Transparent only with creases: 〇, the film turns white: △, the film breaks : X was evaluated. Implementation 列 rows 1, 3, 5, 7, 8, 11, 13, 15, 17! / Evaluation results ί or ヽ! The deviation is also ◯, in Comparative Example 1 X, in Comparative Example 3 It was an evaluation result. Industrial applicability

The present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, and a composition containing the thermosetting resin It has industrial applicability as a molded body, a cured body, and an electronic device including them.

Claims

The scope of the claims

a) a polyfunctional phenolic compound represented by the following general formula (I); b) a diamine compound represented by the following general formula (II); and c) an aldehyde compound. A method for producing a thermosetting resin having a dihydrobenzoxazine ring structure.

[Chemical 1]

[Chemical 2]

The thermosetting according to claim 1, wherein X in the general formula (I) is bonded to the para position with respect to the OH groups of the benzene rings on both sides, and the structure of X is any of the following: A method for producing natural rosin.

2. The method for producing a thermosetting resin according to claim 1, wherein X in the general formula (I) has a structure shown below.

[Chemical 4]

[Wherein n represents an integer of 0 to 10. ]

[Chemical 5]

[Wherein n represents an integer of 0 to 10. ]

[Chemical 6]

[Wherein n represents an integer of 0 to 10. ]

a) a polyfunctional phenolic compound represented by the following general formula (I); b) represented by the following general formula (II): A dihydrobenzoxazine ring structure characterized by heating and reacting a aldehyde compound and a monofunctional phenol represented by the following general formula (III): The method for producing a thermosetting resin according to claim 1.

[Chemical 7]

[Chemical 8]

[Chemical 9]

… (III)

In the monofunctional phenolic compound represented by the general formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: The method for producing a thermosetting resin according to claim 6. [Chemical 10]

[n represents an integer of 0 to 10. ]

In the monofunctional phenolic compound represented by the general formula (III), the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: The method for producing a thermosetting resin according to claim 6.

[Chemical 11]

2. The method for producing a thermosetting resin according to claim 1, wherein the Y force in the general formula (II) is a group represented by the following formula.

[Chemical 12]

I ³

— 0-CH ^ C-CH O—

2 I ²

CH ₃

10. The method for producing a thermosetting resin according to claim 1, wherein Y in the general formula (II) contains one benzene ring.

[11] Y in the general formula (II) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta or para position with respect to the NH groups of the benzene rings on both sides thereof. Claim

2

10. A method for producing a thermosetting resin according to 10.

[Chemical 13]

12. The method for producing a thermosetting resin according to claim 1, wherein Y in the general formula (II) contains at least two benzene rings.

[13] The Y in the general formula (II) is one or more groups selected from the group of the following formulas, and is bonded to the meta or para position with respect to the NH groups of the benzene rings on both sides of Y. Item 12

2

A method for producing a thermosetting resin described in 1.

[Chemical 14]

A thermosetting resin characterized by being a thermosetting resin having a dihydrobenzoxazine structure represented by the following general formula (IV).

[Chemical 15]

V)

[Wherein, X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X.

X in the general formula (IV) has a structure of any one of the following groups of X :, and Y in the general formula (IV) has a structure of any of the following groups of Y: The thermosetting resin according to item 14.

[Chemical 16]

[16] A thermosetting composition comprising at least the thermosetting resin according to claim 14.

[17] A molded product obtained by semi-curing or not curing the thermosetting composition according to claim 16.

[18] A cured product obtained from the thermosetting resin according to claim 14.

[19] A cured product obtained from the thermosetting composition according to claim 16.

[20] An electronic component comprising the cured body according to claim 18 or 19.

[21] A thermosetting resin manufactured by the manufacturing method according to claim 1.

[22] A thermosetting composition comprising at least the thermosetting resin according to claim 21.

[23] A molded product obtained by semi-curing or not curing the thermosetting composition according to claim 22.

[24] A cured product obtained from the thermosetting resin according to claim 21.

[25] A cured product obtained from the thermosetting composition according to claim 22.

[26] An electronic component comprising the cured body according to claim 24 or 25.